Liu Zai-Qun
Department of Organic Chemistry, College of Chemistry, Jilin University, Changchun 130021, China.
Curr Org Synth. 2019;16(3):328-341. doi: 10.2174/1570179416666190328233710.
The Wieland-Miescher ketone consists of a couple of enantiomers of 9-methyl- Δ5(10)-octalin-1,6-dione, in which the configuration at 9-position is S- or R-type. The Robinson annulation of 2-methyl-1,3-cyclohexanedione with methyl vinyl ketone is able to afford the Wieland-Miescher ketone. As widely used in the total synthesis, the Wieland-Miescher ketone is treated at the beginning of total synthesis, and protocols for treating the Wieland-Miescher ketone are worthy to be addressed.
The presented review provides the progress of the usage of Wieland-Miescher ketone for the total synthesis, while treatments on C=C and C=O in the Wieland-Miescher ketone at the beginning of total synthesis are exemplified herein.
Modifications of the Wieland-Miescher ketone are composed of oxidation, reduction, and electrophilic or nucleophilic addition. In addition, protection of non-conjugated C=O with glycol or protection of conjugated C=O with ethanedithiol, and the introduction of substituents into α-position of C=C can also be used to modify the structure of the Wieland-Miescher ketone. It is reasonably believed that many novel strategies will be found to treat the Wieland-Miescher ketone in the future total synthesis.
维兰德-米舍尔酮由9-甲基-Δ5(10)-辛二烯-1,6-二酮的一对对映体组成，其中9位的构型为S型或R型。2-甲基-1,3-环己二酮与甲基乙烯基酮的罗宾逊缩环反应能够得到维兰德-米舍尔酮。作为全合成中广泛使用的试剂，维兰德-米舍尔酮在全合成开始时就需要进行处理，其处理方法值得探讨。
本综述介绍了维兰德-米舍尔酮在全合成中的应用进展，并举例说明了在全合成开始时对维兰德-米舍尔酮中碳碳双键和碳氧双键的处理方法。
维兰德-米舍尔酮的修饰包括氧化、还原、亲电或亲核加成。此外，用二醇保护非共轭碳氧双键或用乙二硫醇保护共轭碳氧双键，以及在碳碳双键的α位引入取代基，也可用于修饰维兰德-米舍尔酮的结构。可以合理地认为，在未来的全合成中将会发现许多处理维兰德-米舍尔酮的新策略。
